JPH0776201B2 - Acid amide- and -imide derivatives of biscation and method for producing the same - Google Patents

Acid amide- and -imide derivatives of biscation and method for producing the same

Info

Publication number
JPH0776201B2
JPH0776201B2 JP3502205A JP50220590A JPH0776201B2 JP H0776201 B2 JPH0776201 B2 JP H0776201B2 JP 3502205 A JP3502205 A JP 3502205A JP 50220590 A JP50220590 A JP 50220590A JP H0776201 B2 JPH0776201 B2 JP H0776201B2
Authority
JP
Japan
Prior art keywords
sodium
tetra
borate
formula
acid amide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP3502205A
Other languages
Japanese (ja)
Other versions
JPH05501717A (en
Inventor
マッハホールト・ハンス―トビアス
シースレル・ジークフリート
ギッツェル・イエルク
ディーツ・エルヴィン
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of JPH05501717A publication Critical patent/JPH05501717A/en
Publication of JPH0776201B2 publication Critical patent/JPH0776201B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/56—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having carbon atoms of carboxamide groups bound to carbon atoms of carboxyl groups, e.g. oxamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/192—Radicals derived from carboxylic acids from aromatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/034—Charge control agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/09741—Organic compounds cationic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/0975—Organic compounds anionic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/09758—Organic compounds comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Fuel Cell (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Description

【発明の詳細な説明】 本発明の対象は、新規のビスカチオンの酸アミド−およ
び−イミド誘導体並びにその製造方法である。詳細に
は、本発明は一般式（Ｉ） 〔式中、R1〜R8は互いに無関係に水素原子または低級ア
ルキル基、例えばメチル−、エチル−、ｎ−プロピル
−、イソ−プロピル−、第三ブチル−、ペンチル−また
はヘキシル基であり、その際に残基R1とR2またはR4とR5
は互いに無関係に、ＫまたはＫ′を組入れて閉環してイ
ミダゾール−、ピペリジン−またはモリホリン環系を形
成していてもよく、 ＡおよびＡ′は式 −(CH2)n− （式中、ｎは１〜10の数である。） で表されるアルキレン基であるか；またはＡおよびR1、
R2またはR3はR7、ＫおよびＮおよび／またはＡ′および
R4、R5またはR6はR8、Ｋ′およびＮと一緒にピペリジン
環系を形成し； ＫおよびＫ′は各々窒素原子であり； W1はそれぞれ炭素原子数１〜６のアルキレンまたはエー
テル−ブリッジ、式−Ｃ（CH2）−CH2−または−CH2−
Ｃ（OH）（COOH）−CH2−で表される基、フェニレンま
たはシクロヘキシレン基または化学結合でありそして R9〜R12は互いに無関係に脂肪族−、脂環式−、イソ−
またはヘテロ環式−、芳香族−または芳香脂肪族残基−
ただし上記の脂肪族−、脂環式−、芳香族−または芳香
脂肪族残基が炭素原子数１〜４のアルキル−、炭素原子
数１〜４のアルコキシ−またはアリール残基またはハロ
ゲン原子で置換されていてもよい−または弗素原子を意
味する。〕 で表されるビスカチオンの酸アミド−および−イミド誘
導体並びにこれらの化合物の混合物および混合されたア
ニオン類および／またはカチオン類との混合結晶であ
る。DETAILED DESCRIPTION OF THE INVENTION The subject of the present invention is novel acid amide- and -imide derivatives of biscations and a process for their preparation. In particular, the invention relates to the general formula (I) [Wherein R 1 to R 8 are independently of each other a hydrogen atom or a lower alkyl group such as a methyl-, ethyl-, n-propyl-, iso-propyl-, tert-butyl-, pentyl- or hexyl group, The residues R 1 and R 2 or R 4 and R 5
Is independently of one another, K or K 'imidazole ring closure incorporates - piperidine - or morpholine ring system may form a, A and A' has the formula - (CH 2) n - (in wherein, n Is a number from 1 to 10.) or A and R 1 ,
R 2 or R 3 is R 7 , K and N and / or A ′ and
R 4 , R 5 or R 6 together with R 8 , K ′ and N form a piperidine ring system; K and K ′ are each a nitrogen atom; W 1 is each an alkylene having 1 to 6 carbon atoms or ether - bridge, formula -C (CH 2) -CH 2 - or -CH 2 -
C (OH) (COOH) -CH 2 - is a group represented by phenylene or cyclohexylene group or a chemical bond and R 9 to R 12 independently of one another are aliphatic -, cycloaliphatic -, iso -
Or heterocyclic-, aromatic- or araliphatic residue-
However, the above aliphatic-, alicyclic-, aromatic- or araliphatic residue is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aryl residue or a halogen atom. Optionally means-or a fluorine atom. ] An acid amide- and -imide derivative of a bis cation represented by: and a mixture of these compounds and a mixed crystal with a mixed anion and / or cation.

式中、ＡおよびＡ′並びにW1は一方の側ではそれぞれＫ
あるいはＫ′にそしてもう一方の側ではイミド−または
アミド窒素に橋かけされているかまたはそれぞれカルボ
ニル基によって、フェニレン−ブリッジ構成員として1,
2−、1,3−、1,4−位、特に1,3−および1,4−位で、ナ
フチレン−ブリッジ構成員として1,2−〜1,8−並びに2,
3−〜2,8−位でそしてシクロヘキシレン−ブリッジ構成
員が1,2−、1,3−、1,4−位、特に1,3−および1,4−位
で置換されていてもよい。Where A and A ′ and W 1 are K on one side, respectively.
Alternatively, as a phenylene-bridge member, bridged to K'and on the other side to the imide- or amide nitrogen or by a carbonyl group respectively,
At the 2-, 1,3-, 1,4-positions, especially at the 1,3- and 1,4-positions, 1,2- to 1,8- and 2, as naphthylene-bridge members.
Even if substituted in the 3- to 2,8-position and the cyclohexylene-bridge member is in the 1,2-, 1,3-, 1,4-position, especially the 1,3- and 1,4-positions. Good.

上記一般式（Ｉ）〜（III）で表され個々の化合物を以
下に例示する： 上述の一般式（Ｉ）のビスカチオンの酸アミド−および
−イミド誘導体並びにそれらの混合物および混合された
アニオンおよび／またはカチオンとの混合結晶は、一般
式（IV） 〔全式中、R1〜R8、ＡおよびＡ′、ＫおよびＫ′並びに
W1が上述の意味を有しそしてX-が化学量論量の一種以上
のハロゲン−アニオン、メチルスルファート−、エチル
スルファート−、ヒドロゲンスルファート−またはスル
ファート−アニオンを意味する。〕 で表される酸アミド−あるいは−イミド誘導体を、水ま
たは水と酸、例えば酢酸との混合物または水と有機溶
剤、例えばイソプロパノール、イソブタノールまたはメ
チルイソブチルケトンとの混合物中で約10℃〜約90℃、
特に約20℃〜約40℃の温度で硼酸塩と反応させることに
よって製造できる。この場合、上記一般式（Ｉ）の化合
物、化合物混合物または混合結晶は良好な収率で且つ良
好な純度で生じ、反応媒体から濾過によって直接的に単
離できる。The individual compounds represented by the above general formulas (I) to (III) are exemplified below: The above-mentioned acid amide- and -imide derivatives of the biscation of the general formula (I) and their mixtures and mixed crystals with mixed anions and / or cations have the general formula (IV) [In the formula, R 1 to R 8 , A and A ', K and K', and
W 1 has the abovementioned meaning and X − represents a stoichiometric amount of one or more halogen-anions, methylsulfate-, ethylsulfate-, hydrogensulfate- or sulphate-anions. An acid amide- or -imide derivative represented by the following formula in water or a mixture of water and an acid such as acetic acid or a mixture of water and an organic solvent such as isopropanol, isobutanol or methyl isobutyl ketone at about 10 ° C to about 10 ° C. 90 ℃,
In particular, it can be produced by reacting with a borate at a temperature of about 20 ° C to about 40 ° C. In this case, the compounds of the above general formula (I), compound mixtures or mixed crystals occur in good yield and in good purity and can be isolated directly from the reaction medium by filtration.

一般式（IV）の化合物の製造は公知の方法で行いそして
文献に詳細に説明されている（例えば、Houben-Weyl、
“Methoden der Organischen Chemie"、Georg Thieme V
erlag、1985、第E5巻、第２部、第924〜1134頁および
同、1958、第11/2巻、第591〜630頁）。The preparation of compounds of general formula (IV) is carried out by known methods and is explained fully in the literature (eg Houben-Weyl,
"Methoden der Organischen Chemie", Georg Thieme V
erlag, 1985, Volume E5, Part 2, pages 924 to 1134 and ibid, 1958, Volume 11/2, pages 591 to 630).

化合物（IV）の製造は例えば脂肪族−、脂環式−、芳香
脂肪族−またはイソ−あるいはヘテロ環式芳香族ジカル
ボン酸または適当なジカルボン酸誘導体、例えばそれら
のエステル、アミド、酸クロライドまたは酸無水物を、
少なくとも一つの第三アミノ基および少なくとも一つの
第一−または第二アミノ基を含有するアミン類またはア
ミノ化合物と不活性反応媒体中でまたは反応媒体として
の過剰のアミン中で反応させ、次いで無機−または有機
酸にてビス−プロトン化するかあるいは適当な四級化剤
にてビス−四級化することによって行う。化合物（IV）
を製造する為には、原料物質としてジカルボン酸ジハロ
ゲニドまたはジカルボン酸ジエステルを使用するのが特
に有利である。製造方法としては、ジカルボン酸ジエス
テル、特にジメチル−またはジエチルエステルをアミン
にて高温のもとで、生ずるアルコールの留去下にアミノ
リシスするのが特に有利である。Compounds (IV) can be prepared, for example, by using aliphatic-, cycloaliphatic-, araliphatic- or iso- or heterocyclic aromatic dicarboxylic acids or suitable dicarboxylic acid derivatives such as their esters, amides, acid chlorides or acids. Anhydrous,
Reaction with amines or amino compounds containing at least one tertiary amino group and at least one primary- or secondary amino group in an inert reaction medium or in excess of amine as reaction medium, then inorganic- Alternatively, it is bis-protonated with an organic acid or bis-quaternized with a suitable quaternizing agent. Compound (IV)
It is particularly advantageous to use dicarboxylic acid dihalogenides or dicarboxylic acid diesters as starting materials for the preparation of As a method of preparation, it is particularly advantageous to carry out aminolysis of dicarboxylic acid diesters, in particular dimethyl- or diethyl esters, with amines at elevated temperature and with distillation of the alcohol formed.

ビス−プロトン化あるいはビス−四級化の為に原則とし
てあらゆる適当な無機−および有機酸あるいはあらゆる
適当なアルキル化剤が適している。酸として特に適して
いるのは塩酸、硫酸および酢酸である。アルキル化剤と
してはアルキル−ハロゲニドおよびジアルキル−スルフ
ァート、特にメチルクロライド、メチルヨード、ジメチ
ル−およびジエチルスルファートが有利である。アルキ
ル化を実施する為の反応媒体としては不活性反応媒体、
例えばジメチルホルムアミドまたは芳香族炭化水素が特
に適している。しかしながら無水のまたは水含有のアル
コール類、例えばイソブタノールまたは約16重量％の水
含有量のイソブタノール／水−共沸混合物も適してい
る。個々の場合には、四級化を水性媒体中でも行うこと
ができる。For bis-protonation or bis-quaternization, in principle any suitable inorganic and organic acid or any suitable alkylating agent is suitable. Particularly suitable as acids are hydrochloric acid, sulfuric acid and acetic acid. Preferred alkylating agents are alkyl-halogenides and dialkyl-sulfates, especially methyl chloride, methyl iodo, dimethyl- and diethyl sulphate. An inert reaction medium as a reaction medium for carrying out the alkylation,
For example, dimethylformamide or aromatic hydrocarbons are particularly suitable. However, anhydrous or water-containing alcohols such as isobutanol or isobutanol / water-azeotropes with a water content of about 16% by weight are also suitable. In the individual case, the quaternization can also be carried out in an aqueous medium.

例えば、式1.1a,b、1.2a,b、2.1a,b、3.1a,b、4.1a,b、
6.1a,b、6.2a,b、および13a,bの上記化合物は、後記の
原料化合物1.1、1.2、2.1、3.1、4.1、6.1、6.2および1
3.1を ナトリウム−テトラフェニルボラートまたはナトリウム
テトラフルオロボラートと反応させることによって製造
される（後記製造例１〜20参照）。For example, formulas 1.1a, b, 1.2a, b, 2.1a, b, 3.1a, b, 4.1a, b,
The above compounds of 6.1a, b, 6.2a, b, and 13a, b are the starting material compounds 1.1, 1.2, 2.1, 3.1, 4.1, 6.1, 6.2 and 1 described below.
3.1 It is produced by reacting with sodium-tetraphenylborate or sodium tetrafluoroborate (see Production Examples 1 to 20 below).

本発明のビスカチオンのアミド−および−イミド誘導体
は、電子写真記録法の為のトナーおよび現像剤として使
用するのに並びに表面被覆の為の粉末および塗料、特に
電気的または動電学的に噴霧される粉末塗料において電
荷改善剤として使用するのに卓越的に適している。The amide- and -imide derivatives of the biscations of the present invention are powders and paints, especially electrically or electrokinetically sprayed, for use as toners and developers for electrophotographic recording and for surface coating. It is outstandingly suitable for use as a charge improver in powder coatings.

下記の製造例にて本発明を更に説明するのに使用する
が、本発明はこれによって制限されない。The following Preparation Examples are used to further illustrate the present invention, but the present invention is not limited thereto.

製造例１ 149.2g（0.73mol）のテレフタル酸ジクロライドを3.5リ
ットルの水不含トルエン中で攪拌しそして次に冷却下に
180.0g（1.76mol）の３−ジメチルアミノ−１−プロピ
ルアミンを20〜30℃で30分の間に滴加する。この温度で
５時間攪拌し、次いで50〜60℃あるいは70〜80℃にそれ
ぞれ１〜２時間加熱しそして次に４時間加熱還流する。
得られる生成物を20〜30℃で吸引濾過し、トルエンで洗
浄しそして100℃で減圧下に乾燥する。292.4g（0.72mo
l）のビスアミドをビスヒドロクロライドの状態で得
る。生成物を450mlの水に溶解しそして０〜５℃で30分
の間、180gの33％濃度苛性ソーダと混合する。その際に
ビスアミドが粗結晶の状態で沈澱する。０〜５℃で１時
間攪拌した後に生成物を吸引濾過し、90mlの氷水で洗浄
しそして100℃で減圧下に乾燥する。Preparation 1 149.2 g (0.73 mol) of terephthalic acid dichloride are stirred in 3.5 l of water-free toluene and then under cooling.
180.0 g (1.76 mol) of 3-dimethylamino-1-propylamine are added dropwise at 20-30 ° C during 30 minutes. Stir at this temperature for 5 hours, then heat to 50-60 ° C or 70-80 ° C for 1-2 hours respectively and then heat to reflux for 4 hours.
The product obtained is suction filtered at 20-30 ° C., washed with toluene and dried at 100 ° C. under reduced pressure. 292.4g (0.72mo
The bisamide of l) is obtained in the form of bishydrochloride. The product is dissolved in 450 ml of water and mixed with 180 g of 33% strength caustic soda for 30 minutes at 0-5 ° C. At that time, the bisamide is precipitated in the form of crude crystals. After stirring for 1 hour at 0-5 ° C., the product is filtered off with suction, washed with 90 ml of ice water and dried at 100 ° C. under reduced pressure.

収量： 221.2g（理論値の90.7％）化合物1.2、白
色粉末 分子量： 334 融点： 172〜174℃1 H−NMR（DMSO−d6中）:1.65（クインテット、４メチレ
ン−Ｈ）、 2.13（シングレット、12メチル−Ｈ）、 2.28（トルプレット、４メチレン−Ｈ）、 3.30（カルテット、４メチレン−Ｈ）、 7.90（シングレット、４フェニレン−Ｈ）、 8.63（トリプレット、２アミド−Ｈ）ppm。Yield: 221.2 g (90.7% of theory) Compound 1.2 , white powder Molecular weight: 334 Melting point: 172-174 ° C. 1 H-NMR (in DMSO-d 6 ): 1.65 (quintet, 4 methylene-H), 2.13 (singlet) , 12 methyl-H), 2.28 (torpret, 4methylene-H), 3.30 (quartet, 4methylene-H), 7.90 (singlet, 4phenylene-H), 8.63 (triplet, 2 amide-H) ppm.

製造例２ 66.8g（0.2mol）の化合物1.2を1.6リットルのトルエン
中で攪拌しそして20〜30℃で10分の間に100.8g（0.8mo
l）のジメチルスルファートと混合する。20〜30℃で１
時間攪拌し、次いで還流下に５時間加熱する。20〜30℃
に冷却した後に、生成物を吸引濾過し、トルエンで洗浄
しそして減圧室で100℃で乾燥する。Preparation 2 66.8 g (0.2 mol) of compound 1.2 are stirred in 1.6 l of toluene and 100.8 g (0.8 mol) in 10 minutes at 20-30 ° C.
Mix with dimethylsulfate from l). 1 at 20-30 ℃
Stir for hours and then heat at reflux for 5 hours. 20-30 ° C
After cooling to 1, the product is suction filtered, washed with toluene and dried in a vacuum chamber at 100 ° C.

収量： 112.7g（理論値の96.2％）化合物1.1、白
色粉末 分子量： 586 融点： 180℃1 H−NMR（D2O中）:2.18（マルチプレット、４メチレン
−Ｈ）、 3.20（シングレット、18メチル−Ｈ）、 3.50（マルチプレット、８メチレン−Ｈ）、 3.75（シングレット、６メチル−Ｈ）、 7.88（シングレット、４フェニレン−Ｈ）ppm 製造例３ 10.0g（17mmol）の化合物1.1の水溶液100mlに室温で攪
拌下に、50mlの水に13.7g（40mmol）のナトリウム−テ
トラフェニルボラートを溶解した溶液を滴加する。その
際に白色の沈澱物として化合物1.1bが沈澱する。この沈
澱物を吸引濾過し、水で洗浄しそして減圧室で60℃で乾
燥する。Yield: 112.7 g (96.2% of theory) Compound 1.1 , white powder Molecular weight: 586 Melting point: 180 ° C. 1 H-NMR (in D 2 O): 2.18 (multiplet, 4 methylene-H), 3.20 (singlet, 18 Methyl-H), 3.50 (multiplet, 8 methylene-H), 3.75 (singlet, 6 methyl-H), 7.88 (singlet, 4 phenylene-H) ppm Preparation Example 3 100 g of an aqueous solution of compound 1.1 ( 1.1 mmol) (17 mmol) 100 ml A solution of 13.7 g (40 mmol) of sodium-tetraphenylborate in 50 ml of water is added dropwise with stirring at room temperature. At this time, compound 1.1b is precipitated as a white precipitate. The precipitate is suction filtered, washed with water and dried in a vacuum chamber at 60 ° C.

収量： 17.0g（理論値の99.8％）化合物1.1ｂ、白
色粉末 分子量： 1002 融点： 255℃1 H−NMR（DMSO−d6中）:1.98（マルチプレット、４メチ
レン−Ｈ）、 3.03（シングレット、18メチル−Ｈ）、 3.38（マルチプレット、８メチレン−Ｈ）、 6.96（マルチプレット、40フェニル−Ｈ）、 7.95（シングレット、４フェニル−Ｈ）、 8.64（トリプレット、２アミド−Ｈ）ppm。Yield: 17.0 g (99.8% of theory) Compound 1.1 b, white powder Molecular weight: 1002 Melting point: 255 ° C. 1 H-NMR (in DMSO-d 6 ): 1.98 (multipletlet, 4 methylene-H), 3.03 (singlet) , 18 methyl-H), 3.38 (multiplet, 8 methylene-H), 6.96 (multiplet, 40 phenyl-H), 7.95 (singlet, 4 phenyl-H), 8.64 (triplet, 2 amide-H) ppm.

製造例４ ナトリウム−テトラフェニルボラート溶液の替わりに、
50mlの水に4.4g（40mmol）のナトリウム−テトラフルオ
ロボラートを溶解した溶液を使用しそしてこの反応溶液
を30mlに濃縮しそして２℃に冷却する点以外は製造例３
における如く実施する。Production Example 4 Instead of the sodium-tetraphenylborate solution,
Preparation 3 except that a solution of 4.4 g (40 mmol) of sodium tetrafluoroborate in 50 ml of water was used and the reaction solution was concentrated to 30 ml and cooled to 2 ° C.
Carry out as in.

収量： 8.9g（理論値の97.3％）化合物1.1ａ、白
色粉末 分子量： 538 融点： 228℃1 H−NMR（DMSO−d6中）:1.99（マルチプレット、４メチ
レン−Ｈ）、 3.05（シングレット、18メチル−Ｈ）、 3.38（マルチプレット、８メチレン−Ｈ）、 7.93（シングレット、４フェニレン−Ｈ）、 8.62（トリプレット、２アミド−Ｈ）ppm。Yield: 8.9 g (97.3% of theory) Compound 1.1 a, white powder Molecular weight: 538 Melting point: 228 ° C. 1 H-NMR (in DMSO-d 6 ): 1.99 (multipletlet, 4 methylene-H), 3.05 (singlet) , 18 methyl-H), 3.38 (multiplet, 8 methylene-H), 7.93 (singlet, 4 phenylene-H), 8.62 (triplet, 2 amide-H) ppm.

製造例５ 5.0g（15mmol）の化合物1.2を、50mlの水に懸濁させそ
してpH7に達するまで2Nの酢酸と混合し、その際にアミ
ンが溶解する。次いで50mlの水に13.7g（40mmol）のナ
トリウム−テトラフェニルボラートを溶解した溶液を滴
加し、その際に生成物が濃厚な白色沈澱物として沈澱す
る。この反応混合物を室温で30分攪拌し、沈澱物を吸引
濾過し、水で洗浄しそして減圧室で60℃で乾燥する。Preparation 5 5.0 g (15 mmol) of compound 1.2 are suspended in 50 ml of water and mixed with 2N acetic acid until a pH of 7 is reached, whereupon the amine dissolves. Then a solution of 13.7 g (40 mmol) of sodium-tetraphenylborate in 50 ml of water is added dropwise, the product precipitating as a thick white precipitate. The reaction mixture is stirred at room temperature for 30 minutes, the precipitate is suction filtered, washed with water and dried at 60 ° C. in a vacuum chamber.

収量： 14.5g（理論値の99.2％）化合物1.2ｂ、白
色粉末 分子量： 974 融点： 197℃1 H−NMR（DMSO−d6中）:1.85（マルチプレット、４メチ
レン−Ｈ）、 2.71（シングレット、12メチル−Ｈ）、 3.00（マルチプレット、４メチレン−Ｈ）、 3.35（マルチプレット、４メチレン−Ｈ）、 6.96（マルチプレット、40フェニル−Ｈ）、 7.93（シングレット、４フェニレン−Ｈ）、 8.63（トリプレット、２アミド−Ｈ）ppm。Yield: 14.5 g (99.2% of theory) Compound 1.2 b, white powder Molecular weight: 974 Melting point: 197 ° C. 1 H-NMR (in DMSO-d 6 ): 1.85 (multipletlet, 4 methylene-H), 2.71 (singlet) , 12 methyl-H), 3.00 (multiplet, 4 methylene-H), 3.35 (multiplet, 4 methylene-H), 6.96 (multiplet, 40 phenyl-H), 7.93 (singlet, 4 phenylene-H), 8.63 (triplet, 2 amide-H) ppm.

製造例６ 109.5g（0.75mol）のジメチル−スクシナートを459g
（4.5mol）の３−ジメチルアミノ−１−プロピルアミン
に溶解する。次いで還流下に10時間加熱する。沸騰温度
が速やかに開始されるメタノール放出によって著しく低
下する為に、メタノール／アミン−混合物の時々の留去
によって気相の温度が125℃以上に維持されるように注
意する。反応時間の終わり頃に、気相の温度は130℃以
上である。反応の過程で約200gのメタノール／アミン−
混合物が留去される。その後に20〜30℃に冷却しそして
結晶化する反応生成物を吸引濾過する。濾液からベンジ
で三倍に希釈することによって更に生成物を沈澱させ
る。生成物をアミン不含状態になるまでベンジンで洗浄
しそして減圧室で100℃で乾燥する。Production Example 6 459 g of 109.5 g (0.75 mol) of dimethyl-succinate
Dissolve in (4.5 mol) 3-dimethylamino-1-propylamine. Then heat at reflux for 10 hours. Care should be taken that the temperature of the gas phase is maintained above 125 ° C by the occasional evaporation of the methanol / amine-mixture, as the boiling temperature is significantly reduced by the rapidly initiated methanol release. Towards the end of the reaction time, the gas phase temperature is above 130 ° C. About 200 g of methanol / amine during the course of the reaction
The mixture is distilled off. Thereafter, it is cooled to 20-30 ° C. and the reaction product which crystallizes is filtered off with suction. Further product is precipitated from the filtrate by three-fold dilution with benzi. The product is washed with benzine until amine-free and dried at 100 ° C. in a vacuum chamber.

収量： 188.0g（理論値の87.6％）化合物6.2、白
色粉末 分子量： 286 融点： 126〜128℃1 H−NMR（DMSO−d6中）:1.48（クインテット、４メチレ
ン−Ｈ）、 2.08（シングレット、12メチル−Ｈ）、 2.20（トリプレット、４メチレン−Ｈ）、 2.25（シングレット、４メチレン−Ｈ）、 3.05（カルテット、４メチレン−Ｈ）、 7.78（トリプレット、２アミド−Ｈ）ppm。Yield: 188.0 g (87.6% of theory) compound 6.2, white powder Molecular weight: 286 mp: 126~128 ℃ 1 H-NMR (in DMSO-d 6): 1.48 (quintet, 4 methylene -H), 2.08 (singlet , 12 methyl-H), 2.20 (triplet, 4methylene-H), 2.25 (singlet, 4methylene-H), 3.05 (quartet, 4methylene-H), 7.78 (triplet, 2 amide-H) ppm.

製造例７ 85.8g（0.3mol）の化合物6.2を610mlの水不含ジメチル
ホルムアミドに導入する。室温で速やかに透明な溶液が
生じる。次いで30〜40℃で約15分の間に189g（1.5mol）
のジメチルスルファートを滴加する。短時間後に、60℃
に加温した際に良好に攪拌できる懸濁液に転化する濃厚
な結晶スラッジが生じる。60〜70℃で５時間、後攪拌し
そして生成物を０〜５℃に冷却した後に吸引濾過する。
徹底滴にトルエンで洗浄しそして減圧室で100℃で乾燥
する。Preparation 7 85.8 g (0.3 mol) of compound 6.2 are introduced into 610 ml of water-free dimethylformamide. A clear solution rapidly forms at room temperature. Then 189g (1.5mol) in about 15 minutes at 30-40 ℃
Of dimethylsulfate is added dropwise. After a short time, 60 ℃
Thick crystalline sludge, which when converted to a well-stirred suspension, is produced when heated to room temperature. After stirring for 5 hours at 60 to 70 ° C. and cooling the product to 0 to 5 ° C., suction filtration is carried out.
Thoroughly wash with toluene and dry in a vacuum chamber at 100 ° C.

収量： 151.0g（理論値の93.6％）化合物6.1、白
色粉末 分子量： 538 融点： 152℃1 H−NMR（DMSO−d6中）:1.85（マルチプレット、４メチ
レン−Ｈ）、 2.33（シングレット、４メチレン−Ｈ）、 3.05（シングレット、18メチル−Ｈ）、 3.20（マルチプレット、８メチレン−Ｈ）、 3.40（シングレット、６メチル−Ｈ）、 7.95（トリプレット、２−アミド−Ｈ）ppm。Yield: 151.0 g (93.6% of theory) compound 6.1, white powder Molecular weight: 538 mp: 152 ℃ 1 H-NMR (in DMSO-d 6): 1.85 (multiplet, 4 methylene -H), 2.33 (singlet, 4 methylene-H), 3.05 (singlet, 18 methyl-H), 3.20 (multiplet, 8 methylene-H), 3.40 (singlet, 6 methyl-H), 7.95 (triplet, 2-amido-H) ppm.

製造例８ 化合物1.1の替わりに10.0g（18.5mmol）の化合物6.1を
使用する点以外は製造例３における如く実施する。Preparative Example 8 The procedure of Preparative Example 3 is repeated except that 10.0 g (18.5 mmol) of Compound 6.1 is used instead of Compound 1.1 .

収量： 17.3g（理論値の98.0％）化合物6.1ｂ、白
色粉末 分子量： 954 融点： 245℃1 H−NMR（DMSO−d6中）:1.81（マルチプレット、４メチ
レン−Ｈ）、 2.37（シングレット、４メチレン−Ｈ）、 3.02（シングレット、18メチル−Ｈ）、 3.12（カルテット、４メチレン−Ｈ）、 3.24（マルチプレット、４メチレン−Ｈ）、 6.97（マルチプレット、40フェニル−Ｈ）、 7.90（トリプレット、２アミド−Ｈ）ppm。Yield: 17.3 g (98.0% of theory) Compound 6.1 b, white powder Molecular weight: 954 mp: 245 ℃ 1 H-NMR (in DMSO-d 6): 1.81 (multiplet, 4 methylene -H), 2.37 (singlet 4 methylene-H), 3.02 (singlet, 18 methyl-H), 3.12 (quartet, 4 methylene-H), 3.24 (multiplet, 4 methylene-H), 6.97 (multiplet, 40 phenyl-H), 7.90 (Triplet, 2 amide-H) ppm.

製造例９ 化合物1.2の替わりに5.0g（17.5mmol）の化合物6.2を使
用する点以外は製造例５における如く実施する。Preparation 9 The procedure is as in Preparation 5 except that 5.0 g (17.5 mmol) of compound 6.2 is used instead of compound 1.2 .

収量： 16.7g（理論値の96.9％）化合物6.2ｂ、白
色粉末 分子量： 926 融点： 183℃1 H−NMR（DMSO−d6中）:1.72（マルチプレット、４メチ
レン−Ｈ）、 2.38（シングレット、４メチレン−Ｈ）、 2.95（マルチプレット、４メチレン−Ｈ）、 3.12（カルテット、４メチレン−Ｈ）、 7.01（マルチプレット、40フェニル−Ｈ）、 7.92（トリプレット、２アミド−Ｈ）ppm。Yield: 16.7 g (96.9% of theory) Compound 6.2 b, white powder Molecular weight: 926 mp: 183 ℃ 1 H-NMR (in DMSO-d 6): 1.72 (multiplet, 4 methylene -H), 2.38 (singlet 4methylene-H), 2.95 (multiplet, 4methylene-H), 3.12 (quartet, 4methylene-H), 7.01 (multiplet, 40phenyl-H), 7.92 (triplet, 2 amide-H) ppm.

製造例10 化合物1.1の替わりに10.0g（17mmol）の化合物3.1を使
用する点以外は製造例３における如く実施する。Preparation 10 The procedure is as in Preparation 3 except that 10.0 g (17 mmol) of compound 3.1 is used instead of compound 1.1 .

収量： 7.8g（理論値の45.5％）化合物3.1ｂ、白
色粉末 分子量： 1008 融点： 255℃1 H−NMR（DMSO−d6中）:1.35（マルチプレット、４メチ
レン−Ｈ）、 1.79（マルチプレット、８シクロヘキシレン−
Ｈ）、 2.08（マルチプレット、２シクロヘキシレン−
Ｈ）、 3.01（シングレット、18メチル−Ｈ）、 3.09（マルチプレット、４メチレン−Ｈ）、 3.25（マルチプレット、４メチレン−Ｈ）、 7.00（マルチプレット、40フェニル−Ｈ）、 7.81（トリプレット、２アミド−Ｈ）ppm。Yield: 7.8 g (45.5% of theory) Compound 3.1 b, white powder Molecular weight: 1008 mp: 255 ℃ 1 H-NMR (in DMSO-d 6): 1.35 (multiplet, 4 methylene -H), 1.79 (Multi Pret, 8 cyclohexylene-
H), 2.08 (multiplet, 2 cyclohexylene-
H), 3.01 (singlet, 18 methyl-H), 3.09 (multiplet, 4 methylene-H), 3.25 (multiplet, 4 methylene-H), 7.00 (multiplet, 40 phenyl-H), 7.81 (triplet, 2 amide-H) ppm.

製造例11 101.5g（0.5mol）のテレフタル酸ジクロライドを2.3リ
ットルのトルエンに溶解しそして20〜30℃に冷却しなが
ら120g（1.2mol）のＮ−メチルピペラジンを滴加する。
20〜30℃で１時間攪拌し、次いで還流するまで２時間に
亘って加熱しそして還流下に４時間煮沸する。室温に冷
却した後に生成物を吸引濾過し、トルエンで洗浄しそし
て乾燥する。乾燥した生成物を400mlの水に溶解し、活
性炭および珪藻土できれいにしそして33％濃度苛性ソー
ダを添加してビスアミドを沈澱させる。このビスアミド
を吸引濾過し、水で洗浄しそして100℃で減圧下に乾燥
する。乾燥した66gのこのビスアミドを640mlのジメチル
ホルムアミドに溶解しそして76ml（0.8mol）のジメチル
スルファートを室温で僅かに冷却しながら15分に亘って
滴加する。次に60〜70℃で５時間加温し、次いで生成物
を０〜５℃で吸引濾過し、トルエンで洗浄しそして100
℃で減圧下に乾燥する。Preparation 11 101.5 g (0.5 mol) of terephthalic acid dichloride are dissolved in 2.3 l of toluene and 120 g (1.2 mol) of N-methylpiperazine are added dropwise with cooling to 20-30 ° C.
Stir at 20-30 ° C for 1 hour, then heat to reflux for 2 hours and boil under reflux for 4 hours. After cooling to room temperature, the product is suction filtered, washed with toluene and dried. The dried product is dissolved in 400 ml of water, cleaned with activated carbon and diatomaceous earth and the 33% strength caustic soda is added to precipitate the bisamide. The bisamide is filtered off with suction, washed with water and dried at 100 ° C. under reduced pressure. Dry 66 g of this bisamide are dissolved in 640 ml of dimethylformamide and 76 ml (0.8 mol) of dimethylsulfate are added dropwise over 15 minutes at room temperature with slight cooling. Then warm at 60-70 ° C for 5 hours, then suction filter the product at 0-5 ° C, wash with toluene and 100
Dry under reduced pressure at ° C.

収量： 109g（定量的収率）化合物13.1、白色粉末 分子量： 582 融点： ＞300℃1 H−NMR（D2O中）:3.28（シングレット、12メチル−
Ｈ）、 3.53（マルチプレット、8Hピレラジノ−Ｈ）、 3.73（シングレット、メチルスルファート−アニ オンのメチル−Ｈ、メチルスルファートの大部分は 加水分解されてヒドロゲンスルファートに成ってい る）、 3.88（マルチプレット、４ピペラジノ−Ｈ）、 4.13（マルチプレット、４ピペラジノ−Ｈ）、 7.60（シングレット、４フェニレン−Ｈ）ppm 製造例12 5.0g（9mmol）の化合物17.1を室温で20mlの水に溶解す
る。Yield: 109 g (quantitative yield) Compound 13.1 , white powder Molecular weight: 582 Melting point:> 300 ° C. 1 H-NMR (in D 2 O): 3.28 (singlet, 12 methyl-
H), 3.53 (multipletlets, 8H pyreradino-H), 3.73 (singlet, methyl-H of methylsulfate-anion, most of methylsulfate is hydrolyzed to hydrogensulfate), 3.88 (Multiplet, 4 piperazino-H), 4.13 (Multiplet, 4 piperazino-H), 7.60 (singlet, 4phenylene-H) ppm Preparation Example 12 5.0 g (9 mmol) of compound 17.1 was added to 20 ml of water at room temperature. Dissolve.

次に2.2g（20mmol）のナトリウム−テトラフルオロボラ
ートを25mlの水にゆっくり添加し、その際に反応混合物
は沈澱した結晶の為に非常に濃厚に成る。水で250mlに
希釈しそして無色のこの結晶を濾過する。水で洗浄した
後にこの生成物を減圧下に100℃で乾燥する。Then 2.2 g (20 mmol) of sodium tetrafluoroborate are slowly added to 25 ml of water, the reaction mixture becoming very thick due to the precipitated crystals. Dilute to 250 ml with water and filter off the colorless crystals. After washing with water, the product is dried under reduced pressure at 100 ° C.

収量： 3.8g（理論値の79.1％）化合物13.1ａ、白
色結晶 分子量： 534 融点： ＞300℃1 H−NMR（DMSO−d6中）:3.20（シングレット、12メチル
−Ｈ）、 3.48（シングレット、８ピペラジノ−Ｈ）、 3.83（シングレット、８ピペラジノ−Ｈ）、 7.56（シングレット、４フェニレン−Ｈ）ppm。Yield: 3.8 g (79.1% of theory) compound 13.1 a, white crystalline molecular weight: 534 mp:> 300 ℃ 1 H-NMR ( in DMSO-d 6): 3.20 (singlet, 12-methyl -H), 3.48 (singlet , 8 piperazino-H), 3.83 (singlet, 8 piperazino-H), 7.56 (singlet, 4phenylene-H) ppm.

製造例13 ナトリウム−テトラフルオロボラートの替わりに、20ml
の水に溶解した70g（20mmol）のナトリウム−テトラフ
ェニルボラートを使用して、製造例20における如く実施
する。Production Example 13 Instead of sodium-tetrafluoroborate, 20 ml
Is carried out as in Preparation 20 using 70 g (20 mmol) of sodium-tetraphenylborate dissolved in water.

収量： 7.6g（理論値の84.6％）化合物13.1ｂ、白
色粉末 分子量： 998 融点： 292（分解）1 H−NMR（DMSO−d6中）:3.19（シングレット、12メチル
−Ｈ）、 3.46（シングレット、８ピペラジノ−Ｈ）、 3.82（シングレット、８ピペラジノ−Ｈ）、 7.03（マルチプレット、40フェニル−Ｈ）、 7.55（シングレット、４フェニレン−Ｈ）ppm。Yield: 7.6 g (84.6% of theory) Compound 13.1b , white powder Molecular weight: 998 Melting point: 292 (decomposition) 1 H-NMR (in DMSO-d 6 ): 3.19 (singlet, 12 methyl-H), 3.46 ( Singlet, 8 piperazino-H), 3.82 (singlet, 8 piperazino-H), 7.03 (multiplet, 40 phenyl-H), 7.55 (singlet, 4 phenylene-H) ppm.

本発明は、請求の範囲に記載のビスカチオンの酸アミド
−および−イミド誘導体並びにその製造方法に関するも
のであるが、実施の態様として以下を挿入する： 「１）式（Ｉ） 〔式中、互いに無関係にR1、R4がＨ、CH3、C2H5であ
り、互いに無関係にR2、R3、R5およびR6がCH3、C2H5で
あり、ｎが１〜５でありそしてアニオンがBF4 -またはＢ
（フェニル）4 -である。〕 で表される請求項１〜６の少なくとも一つに記載のビス
カチオンの酸アミド誘導体。The present invention relates to acid amide- and -imide derivatives of a biscation described in the claims and a method for producing the same, and the following is inserted as an embodiment: "1" Formula (I) [Wherein R 1 and R 4 independently of each other are H, CH 3 and C 2 H 5 , and independently of each other R 2 , R 3 , R 5 and R 6 are CH 3 and C 2 H 5 , n is 1 to 5 and the anion is BF 4 - or B
(Phenyl) 4 - a. ] The acid amide derivative of the biscation of Claim 1 represented by at least 1-6.

２）式（Ｉ） 〔式中、互いに無関係にR1、R4がＨ、CH3、C2H5であ
り、互いに無関係にR2、R3、R5およびR6がCH3、C2H5で
あり、ｍが１〜８であり、ｎが２または３でありそして
アニオンがBF4 -またはＢ（フェニル）4 -である。〕 で表される請求項１〜６の少なくとも一つに記載のビス
カチオンの酸アミド誘導体。2) Formula (I) [Wherein R 1 and R 4 independently of each other are H, CH 3 and C 2 H 5 , and independently of each other R 2 , R 3 , R 5 and R 6 are CH 3 and C 2 H 5 , m is 1-8, n is 2 or 3 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid amide derivative of the biscation of Claim 1 represented by at least 1-6.

３）式（II） 〔式中、互いに無関係にR1、R4がＨ、CH3、C2H5であ
り、互いに無関係にR2、R3、R5およびR6がCH3、C2H5で
あり、ｎが２または３でありそしてアニオンがBF4 -また
はＢ（フェニル）4 -である。〕 で表される請求項１〜６の少なくとも一つに記載のビス
カチオンの酸イミド誘導体。3) Formula (II) [Wherein R 1 and R 4 independently of each other are H, CH 3 and C 2 H 5 , and independently of each other R 2 , R 3 , R 5 and R 6 are CH 3 and C 2 H 5 , n is 2 or 3 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid imide derivative of the biscation of Claim 1 represented by at least 1-6.

４）式（II） 〔式中、互いに無関係にR1、R4がＨ、CH3、C2H5であ
り、互いに無関係にR2、R3、R5およびR6がCH3、C2H5で
あり、ｎが２または３でありそしてアニオンがBF4 -また
はＢ（フェニル）4 -である。〕 で表される請求項１〜６の少なくとも一つに記載のビス
カチオンの酸イミド誘導体。4) Formula (II) [Wherein R 1 and R 4 independently of each other are H, CH 3 and C 2 H 5 , and independently of each other R 2 , R 3 , R 5 and R 6 are CH 3 and C 2 H 5 , n is 2 or 3 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid imide derivative of the biscation of Claim 1 represented by at least 1-6.

５）式（II） 〔式中、互いに無関係にR1、R4がＨ、CH3、C2H5であ
り、互いに無関係にR2、R3、R5およびR6がCH3、C2H5で
あり、ｎが２または３でありそしてアニオンがBF4 -また
はＢ（フェニル）4 -である。〕 で表される請求項１〜６の少なくとも一つに記載のビス
カチオンの酸イミド誘導体。5) Formula (II) [Wherein R 1 and R 4 independently of each other are H, CH 3 and C 2 H 5 , and independently of each other R 2 , R 3 , R 5 and R 6 are CH 3 and C 2 H 5 , n is 2 or 3 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid imide derivative of the biscation of Claim 1 represented by at least 1-6.

６）式（Ｉ） 〔式中、互いに無関係にR1、R3がＨ、CH3、C2H5であ
り、互いに無関係にR2、R4がCH3、C2H5でありそしてア
ニオンがBF4 -またはＢ（フェニル）4 -である。〕 で表される請求項１〜６の少なくとも一つに記載のビス
カチオンの酸アミド誘導体。6) Formula (I) Wherein an R 1, R 3 is H, CH 3, C 2 H 5 independently of one another, are CH 3, C 2 H 5 independently R 2, R 4 to each other and anion BF 4 - or B (phenyl) 4 - a. ] The acid amide derivative of the biscation of Claim 1 represented by at least 1-6.

７）請求項７に記載の一般式（IV）〜（VI）の化合物を
水および酢酸、イソプロパノール、イソブタノールまた
はメチルイソブチルケトンより成る混合物中で反応させ
る請求項７に記載の方法。7) The process according to claim 7, wherein the compounds of the general formulas (IV) to (VI) according to claim 7 are reacted in a mixture of water and acetic acid, isopropanol, isobutanol or methyl isobutyl ketone.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 241/08 295/16 Ａ 471/04 １１２ 487/04 １３７ 7019−4Ｃ Ｃ０７Ｆ 5/02 Ａ 7457−4Ｈ 9/54 9155−4Ｈ 9/66 9155−4Ｈ (72)発明者 ギッツェル・イエルク ドイツ連邦共和国、デー―6234 ハッテル スハイム、ドムヘールンストラーセ、２ (72)発明者 ディーツ・エルヴィン ドイツ連邦共和国、デー―6233 ケルクハ イム（タウヌス）、ザンクト―マットホイ ス―ストラーセ、７─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07D 241/08 295/16 A 471/04 112 487/04 137 7019-4C C07F 5/02 A 7457 -4H 9/54 9155-4H 9/66 9155-4H (72) Inventor Gitzel Jörg, Federal Republic of Germany, Day 6234 Hattersheim, Domhernstraße, 2 (72) Inventor Dietz Erwin, Federal Republic of Germany , Day-6233 Kerkheim (Taunus), Sankt-Matte Heus-Strasse, 7

Claims (8)

【特許請求の範囲】[Claims] 【請求項１】一般式Ｉ 〔式中、R1〜R8は互いに無関係に水素原子または低級ア
ルキル基であり、その際に残基R1とR2またはR4とR5は互
いに無関係に、ＫまたはＫ′を組入れて閉環してイミダ
ゾール−、ピペリジン−またはモルホリン環系を形成し
ていてもよく、 ＡおよびＡ′は式 −(CH2)n− （式中、ｎは１〜10の数である。） で表されるアルキレン基であるか；またはＡおよびR1、
R2またはR3はR7、ＫおよびＮおよび／またはＡ′および
R4、R5またはR6はR8、Ｋ′およびＮと一緒にピペリジン
環系を形成し； ＫおよびＫ′は各々窒素原子であり； W1はそれぞれ炭素原子数１〜６のアルキレンまたはエー
テル−ブリッジ、式−Ｃ（＝CH2）−CH2−または−CH2
−Ｃ（OH）（COOH）−CH2−で表される基、フェニレン
またはシクロヘキシレン基または化学結合でありそして R9〜R12は互いに無関係に脂肪族−、脂環式−、イソ−
またはヘテロ環式−、芳香族−または芳香脂肪族残基−
ただし上記の脂肪族−、脂環式−、芳香族−または芳香
脂肪族残基が炭素原子数１〜４のアルキル−、炭素原子
数１〜４のアルコキシ−またはアリール残基またはハロ
ゲン原子で置換されていてもよい−または弗素原子を意
味する。〕 で表されるビスカチオンの酸アミド−および−イミド誘
導体並びにこれらの化合物の混合物および混合されたア
ニオン類および／またはカチオン類との混合結晶。1. A general formula I [In the formula, R 1 to R 8 are independently of each other a hydrogen atom or a lower alkyl group, and the residues R 1 and R 2 or R 4 and R 5 are independent of each other by incorporating K or K '. Table in (wherein, n is a number from 1 to 10.) - cyclized imidazole -, piperidine - or may form a morpholine ring system, a and a 'are the formula - (CH 2) n An alkylene group represented by: or A and R 1 ,
R 2 or R 3 is R 7 , K and N and / or A ′ and
R 4 , R 5 or R 6 together with R 8 , K ′ and N form a piperidine ring system; K and K ′ are each a nitrogen atom; W 1 is each an alkylene having 1 to 6 carbon atoms or ether - bridge, formula -C (= CH 2) -CH 2 - or -CH 2
A group represented by --C (OH) (COOH)-CH 2- , a phenylene or cyclohexylene group or a chemical bond, and R 9 to R 12 are independently of each other aliphatic-, alicyclic-, iso-
Or heterocyclic-, aromatic- or araliphatic residue-
However, the above aliphatic-, alicyclic-, aromatic- or araliphatic residue is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aryl residue or a halogen atom. Optionally means-or a fluorine atom. ] The acid amide- and -imide derivative of the bis cation represented by these, the mixture of these compounds, and the mixed crystal with the mixed anions and / or cations. 【請求項２】R1〜R6は互いに無関係に水素原子または炭
素原子数１〜４のアルキル基であり； R7およびR8がそれぞれ水素原子を意味し； ＡおよびＡ′は互いに無関係にｐ＝１〜４の−(CH2)p−
ブリッジ構成員であり； W1は炭素原子数１〜６のアルキレン基、式−CH2−Ｏ−C
H2−CH2−Ｏ−CH2−のエーテルブリッジ構成員、フェニ
レン−またはシクロヘキシレン基でありそして R9〜R12がフェニル−、ナフチル−、フルオロフェニル
−、クロロフェニル−、メトキシフェニル−、ビフェニ
ル−、ピリジル−またはトルイル残基または弗素原子を
意味する、請求項１に記載のビスカチオンの酸アミド−
および−イミド誘導体。2. R 1 to R 6 are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 7 and R 8 are each a hydrogen atom; A and A ′ are independent of each other. p = 1 to 4 of the - (CH 2) p -
Is a bridge member; W 1 is an alkylene group having 1 to 6 carbon atoms, and has the formula —CH 2 —O—C.
H 2 -CH 2 -O-CH 2 - ether bridge members, phenylene - or cyclohexylene and R 9 to R 12 is phenyl - naphthyl -, fluorophenyl -, chlorophenyl -, methoxyphenyl -, biphenyl An acid amide of a biscation according to claim 1, which means a-, pyridyl- or toluyl residue or a fluorine atom.
And-imido derivatives. 【請求項３】式Ｉ 〔式中、R1およびR4は互いに無関係にＨ、CH3またはC2H
5であり、R2、R3、R5およびR6がCH3またはC2H5であり、
ｎは１〜５でありそしてアニオンがBF4 -またはＢ（フェ
ニル）4 -である。〕 で表される、請求項１または２に記載のビスカチオンの
酸アミド−および−イミド誘導体。3. Formula I [Wherein R 1 and R 4 are independently of each other H, CH 3 or C 2 H
5 and R 2 , R 3 , R 5 and R 6 are CH 3 or C 2 H 5 ,
n is 1 to 5 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid amide- and -imide derivative of the bis cation of Claim 1 or 2 represented by these. 【請求項４】式Ｉ 〔式中、R1およびR4は互いに無関係にＨ、CH3またはC2H
5であり、R2、R3、R5およびR6がCH3またはC2H5であり、
ｍは１〜６であり、ｎが２または３でありそしてアニオ
ンがBF4 -またはＢ（フェニル）4 -である。〕 で表される、請求項１または２に記載のビスカチオンの
酸アミド−および−イミド誘導体。4. Formula I [Wherein R 1 and R 4 are independently of each other H, CH 3 or C 2 H
5 and R 2 , R 3 , R 5 and R 6 are CH 3 or C 2 H 5 ,
m is 1 to 6, n is 2 or 3 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid amide- and -imide derivative of the bis cation of Claim 1 or 2 represented by these. 【請求項５】式Ｉ 〔式中、R1およびR3は互いに無関係にＨ、CH3またはC2H
5であり、R2およびR4はCH3またはC2H5でありそしてアニ
オンがBF4 -またはＢ（フェニル）4 -である。〕 で表される、請求項１または２に記載のビスカチオンの
酸アミド−および−イミド誘導体。5. Formula I [Wherein R 1 and R 3 are independently of each other H, CH 3 or C 2 H
5 , R 2 and R 4 are CH 3 or C 2 H 5 and the anion is BF 4 − or B (phenyl) 4 − . ] The acid amide- and -imide derivative of the bis cation of Claim 1 or 2 represented by these. 【請求項６】請求項１に記載の一般式（Ｉ）の酸アミド
−および−イミド誘導体または酸アミド−および−イミ
ド誘導体の混合物または混合されたアニオンおよび／ま
たはカチオンとの混合結晶を製造する方法において、一
般式（IV） 〔全式中、R1〜R8、ＡおよびＡ′、ＫおよびＫ′並びに
W1が請求項１に記載の意味を有しそしてX-が化学量論量
の一種以上のハロゲン−アニオン、メチルスルファート
−、エチルスルファート−、ヒドロゲンスルファート−
またはスルファート−アニオンを意味する。〕 で表される酸アミド−あるいは−イミド誘導体を、水ま
たは水と酸との混合物または水と有機溶剤との混合物中
で約10℃〜約90℃の温度で請求項１に記載の一種以上の
硼酸塩と反応させることを特徴とする、上記方法。6. Preparation of a mixture of acid amide- and -imide derivatives or acid amide- and -imide derivatives of the general formula (I) according to claim 1 or mixed crystals with mixed anions and / or cations. In the method, the general formula (IV) [In the formula, R 1 to R 8 , A and A ', K and K', and
W 1 has the meaning according to claim 1 and X − is a stoichiometric amount of one or more halogen-anions, methylsulfate, ethylsulfate, hydrogensulfate-.
Or it means a sulfate-anion. The acid amide- or -imide derivative represented by the formula (1) or more according to claim 1 at a temperature of about 10 ° C to about 90 ° C in water or a mixture of water and an acid or a mixture of water and an organic solvent. The method as described above, which comprises reacting with a borate. 【請求項７】請求項６に記載の一般式（IV）の化合物を
水および酢酸、イソプロパノール、イソブタノールまた
はメチルイソブチルケトンより成る混合物中で反応させ
る請求項６に記載の方法。7. The process according to claim 6, wherein the compound of general formula (IV) according to claim 6 is reacted in a mixture of water and acetic acid, isopropanol, isobutanol or methyl isobutyl ketone. 【請求項８】請求項６に記載の一般式（IV）の化合物
を、ナトリウム−テトラフェニルンボラート、ナトリウ
ム−テトラ−ｏ−フルオロフェニルボラート、ナトリウ
ム−テトラ−ｍ−フルオロフェニルボラート、ナトリウ
ム−テトラ−ｐ−フルオロフェニルボラート、ナトリウ
ム−テトラ−ｏ−クロロフェニルボラート、ナトリウム
−テトラ−ｍ−クロロフェニルボラート、ナトリウム−
テトラ−ｐ−クロロフェニルボラート、ナトリウム−テ
トラ−ｏ−トルイルボラート、ナトリウム−テトラ−ｍ
−トルイルボラート、ナトリウム−テトラ−ｐ−トルイ
ルボラート、ナトリウム−テトラ−１−ナフチルボラー
ト、ナトリウム−テトラ−２−ナフチルボラート、ナト
リウム−テトラ−ｏ−メトキシフェニルボラート、ナト
リウム−テトラ−ｍ−メトキシフェニルボラート、ナト
リウム−テトラ−ｐ−メトキシフェニルボラート、ナト
リウム−テトラ−ｏ−ビフェニルボラート、ナトリウム
−テトラ−ｍ−ビフェニルボラート、ナトリウム−テト
ラ−ｐ−ビフェニルボラート、ナトリウム−テトラベン
ジルボラート、ナトリウム−テトラ−ｏ−ピリジルボラ
ート、ナトリウム−テトラ−ｍ−ピリジルボラート、ナ
トリウム−テトラ−ｐ−ピリジルボラートまたはナトリ
ウム−テトラフルオロボラートと反応させる請求項７に
記載の方法。8. A compound of the general formula (IV) according to claim 6 is added to sodium tetraphenylborate, sodium tetra-o-fluorophenylborate, sodium tetra-m-fluorophenylborate, sodium. -Tetra-p-fluorophenyl borate, sodium-tetra-o-chlorophenyl borate, sodium-tetra-m-chlorophenyl borate, sodium-
Tetra-p-chlorophenyl borate, sodium-tetra-o-toluyl borate, sodium-tetra-m
-Toluyl borate, sodium-tetra-p-toluyl borate, sodium-tetra-1-naphthyl borate, sodium-tetra-2-naphthyl borate, sodium-tetra-o-methoxyphenyl borate, sodium-tetra-m-methoxyphenyl Borate, sodium-tetra-p-methoxyphenylborate, sodium-tetra-o-biphenylborate, sodium-tetra-m-biphenylborate, sodium-tetra-p-biphenylborate, sodium-tetrabenzylborate. 8. The process according to claim 7, which is reacted with sodium tetra-o-pyridyl borate, sodium tetra-m-pyridyl borate, sodium tetra-p-pyridyl borate or sodium tetrafluoroborate.
JP3502205A 1989-12-28 1990-12-17 Acid amide- and -imide derivatives of biscation and method for producing the same Expired - Lifetime JPH0776201B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE3943047 1989-12-28
DE3943047.2 1990-09-05
DE4028121 1990-09-05
DE4028121.3 1990-09-05
PCT/EP1990/002199 WO1991009835A1 (en) 1989-12-28 1990-12-17 Biscationic acid amide and acid imide derivatives and process for preparing them

Publications (2)

Publication Number Publication Date
JPH05501717A JPH05501717A (en) 1993-04-02
JPH0776201B2 true JPH0776201B2 (en) 1995-08-16

Family

ID=25888543

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3502205A Expired - Lifetime JPH0776201B2 (en) 1989-12-28 1990-12-17 Acid amide- and -imide derivatives of biscation and method for producing the same

Country Status (6)

Country Link
US (1) US5329046A (en)
EP (1) EP0507824B1 (en)
JP (1) JPH0776201B2 (en)
CA (1) CA2072597C (en)
DE (1) DE59007528D1 (en)
WO (1) WO1991009835A1 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7511142B2 (en) * 2004-07-28 2009-03-31 Agency For Science, Technology And Research Mediator-modified redox biomolecules for use in electrochemical determination of analyte
US7462720B2 (en) * 2004-09-02 2008-12-09 Agency Science Tech & Res Determination of nucleic acid using electrocatalytic intercalators
US8754114B2 (en) 2010-12-22 2014-06-17 Incyte Corporation Substituted imidazopyridazines and benzimidazoles as inhibitors of FGFR3
DK2861595T5 (en) 2012-06-13 2018-01-15 Incyte Holdings Corp Substituted tricyclic compounds as FGFR inhibitors
WO2014026125A1 (en) 2012-08-10 2014-02-13 Incyte Corporation Pyrazine derivatives as fgfr inhibitors
US9266892B2 (en) 2012-12-19 2016-02-23 Incyte Holdings Corporation Fused pyrazoles as FGFR inhibitors
MX367878B (en) 2013-04-19 2019-09-10 Incyte Holdings Corp Bicyclic heterocycles as fgfr inhibitors.
US10851105B2 (en) 2014-10-22 2020-12-01 Incyte Corporation Bicyclic heterocycles as FGFR4 inhibitors
US9580423B2 (en) 2015-02-20 2017-02-28 Incyte Corporation Bicyclic heterocycles as FGFR4 inhibitors
EP3259269B9 (en) 2015-02-20 2020-03-04 Incyte Corporation Bicyclic heterocycles as fgfr inhibitors
MA41551A (en) 2015-02-20 2017-12-26 Incyte Corp BICYCLIC HETEROCYCLES USED AS FGFR4 INHIBITORS
AR111960A1 (en) 2017-05-26 2019-09-04 Incyte Corp CRYSTALLINE FORMS OF A FGFR INHIBITOR AND PROCESSES FOR ITS PREPARATION
BR112020022392A2 (en) 2018-05-04 2021-02-02 Incyte Corporation solid forms of a fgfr inhibitor and processes for preparing them
JP2021523118A (en) 2018-05-04 2021-09-02 インサイト・コーポレイションＩｎｃｙｔｅ Ｃｏｒｐｏｒａｔｉｏｎ FGFR inhibitor salt
US11628162B2 (en) 2019-03-08 2023-04-18 Incyte Corporation Methods of treating cancer with an FGFR inhibitor
US11591329B2 (en) 2019-07-09 2023-02-28 Incyte Corporation Bicyclic heterocycles as FGFR inhibitors
BR112022007163A2 (en) 2019-10-14 2022-08-23 Incyte Corp BICYCLIC HETEROCYCLES AS FGFR INHIBITORS
WO2021076728A1 (en) 2019-10-16 2021-04-22 Incyte Corporation Bicyclic heterocycles as fgfr inhibitors
JP2023505258A (en) 2019-12-04 2023-02-08 インサイト・コーポレイション Tricyclic heterocycles as FGFR inhibitors
IL293001A (en) 2019-12-04 2022-07-01 Incyte Corp Derivatives of an fgfr inhibitor
US12012409B2 (en) 2020-01-15 2024-06-18 Incyte Corporation Bicyclic heterocycles as FGFR inhibitors
EP4323405A1 (en) 2021-04-12 2024-02-21 Incyte Corporation Combination therapy comprising an fgfr inhibitor and a nectin-4 targeting agent
JP2024522189A (en) 2021-06-09 2024-06-11 インサイト・コーポレイション Tricyclic Heterocycles as FGFR Inhibitors

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299982A (en) * 1977-07-11 1981-11-10 Petrolite Corporation Quaternaries of hydroxyalkylaminoalkylamides
JPS5833543B2 (en) * 1979-06-28 1983-07-20 コニカ株式会社 photographic material
EP0026157B1 (en) * 1979-09-20 1984-06-13 Ciba-Geigy Ag Quaternary ammonium salts from diepoxydes and diamines, their preparation and their use
CH650767A5 (en) * 1981-12-17 1985-08-15 Ciba Geigy Ag AMINE GROUP-CONTAINING CARBONIC ACID AMIDES AND THEIR USE AS HARDENERS FOR EPOXY RESINS.
US4737497A (en) * 1983-04-12 1988-04-12 Zenyaki Kogyo Kabushiki Kaisha Bis-dioxopiperazine derivatives, antitumor agents comprising them and compositions containing them
DE3375135D1 (en) * 1983-04-15 1988-02-11 Miranol Inc Polyquaternary ammonium compounds and cosmetic compositions containing them
GB8802646D0 (en) * 1988-02-05 1988-03-02 Croda Int Plc Humectants

Also Published As

Publication number Publication date
EP0507824B1 (en) 1994-10-19
CA2072597A1 (en) 1991-06-29
JPH05501717A (en) 1993-04-02
US5329046A (en) 1994-07-12
EP0507824A1 (en) 1992-10-14
CA2072597C (en) 1998-09-22
DE59007528D1 (en) 1994-11-24
WO1991009835A1 (en) 1991-07-11

Similar Documents

Publication Publication Date Title
JPH0776201B2 (en) Acid amide- and -imide derivatives of biscation and method for producing the same
US20080177085A1 (en) Process for the Synthesis of a CPLA2 Inhibitor
US4716243A (en) α-(o-chlorophenyl)-aminomethylene-β-formylaminopropionitrile
PL188819B1 (en) Novel substituted [2-(1-piperazinyl)ethoxy] methyl compounds
US4675432A (en) Method for the preparation of anilinofumarate
JP3364895B2 (en) Production of folic acid
JP2802318B2 (en) Ammonium and iminium compounds and their preparation
US6087506A (en) Preparation of hetero arylcarboxamides
JPS63258442A (en) Production of tetrafluorophthalic acid
JPH10139781A (en) Production of diketopyrrolopyrrole carboxylic acid, and ester and amide thereof
CA2001988C (en) Hydroxylamine derivatives
JP3618515B2 (en) Method for producing triarylboraneamine complex
JP2842441B2 (en) Method for producing dialkyl oxal acetates
JP2812761B2 (en) Process for the preparation of anilino fumarate via chloromaleate or chlorofumarate or mixtures thereof
JP3486669B2 (en) Tetraamino compound and method for producing the same
JP2603328B2 (en) Method for producing 2-cyano-3-aminoacrylonitrile derivative
JPH0140833B2 (en)
CA1305722C (en) Process for producing tetrafluorophthalic acid
US4847405A (en) Method for the preparation of anilinofumarate [quinoline-2,3- dicarboxylic]
US6084134A (en) Process for preparing 9-anthracenecarbaldehyes
DE4040469A1 (en) New bis:cationic acid amide and imide substd. borate cpds. - prepd. from cpd. with different anion, useful as colourless charge transfer agent in toner
EP0881210B1 (en) Process for the production of N,N-dialkylaminophenyl alkanols
SU196647A1 (en) METHOD FOR OBTAINING AMINOETHYL ETHERAL CYCLOHEXANES
JP3749564B2 (en) Method for producing tetralin carboxylic acid ester
JPH03200747A (en) Production of n-alkyl-4-t-butylbenzylamine derivative